US4147886A - Process for the preparation of ethynyl-β-ionol - Google Patents

Process for the preparation of ethynyl-β-ionol Download PDF

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Publication number
US4147886A
US4147886A US05/808,509 US80850977A US4147886A US 4147886 A US4147886 A US 4147886A US 80850977 A US80850977 A US 80850977A US 4147886 A US4147886 A US 4147886A
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US
United States
Prior art keywords
ionol
ethynyl
alkali metal
solution
acetylene
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
US05/808,509
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English (en)
Inventor
Hermann Wiederkehr
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Roche Vitamins Inc
Original Assignee
Hoffmann La Roche Inc
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
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Assigned to ROCHE VITAMINS INC. reassignment ROCHE VITAMINS INC. ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: HOFFMANN-LA ROCHE INC.
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C403/00—Derivatives of cyclohexane or of a cyclohexene or of cyclohexadiene, having a side-chain containing an acyclic unsaturated part of at least four carbon atoms, this part being directly attached to the cyclohexane or cyclohexene or cyclohexadiene rings, e.g. vitamin A, beta-carotene, beta-ionone
    • C07C403/06—Derivatives of cyclohexane or of a cyclohexene or of cyclohexadiene, having a side-chain containing an acyclic unsaturated part of at least four carbon atoms, this part being directly attached to the cyclohexane or cyclohexene or cyclohexadiene rings, e.g. vitamin A, beta-carotene, beta-ionone having side-chains substituted by singly-bound oxygen atoms
    • C07C403/08—Derivatives of cyclohexane or of a cyclohexene or of cyclohexadiene, having a side-chain containing an acyclic unsaturated part of at least four carbon atoms, this part being directly attached to the cyclohexane or cyclohexene or cyclohexadiene rings, e.g. vitamin A, beta-carotene, beta-ionone having side-chains substituted by singly-bound oxygen atoms by hydroxy groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2601/00—Systems containing only non-condensed rings
    • C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
    • C07C2601/16—Systems containing only non-condensed rings with a six-membered ring the ring being unsaturated

Definitions

  • the present invention is concerned with a process for the manufacture of ethynyl- ⁇ -ionol.
  • Ethynyl- ⁇ -ionol is an intermediate used in the preparation of vitamin A.
  • alkali metal hydroxides may be employed in the process of this invention with sodium and potassium hydroxide being preferred. Potassium hydroxide is particularly preferred.
  • a preferred embodiment of the process in accordance with the invention consists in that the reaction is carried out in the temperature range between about -20° and about +5° C., preferably at about 0° C., and at pressures varying from 1.5 atmospheres to 9.5 atmospheres, preferably 8 atmospheres.
  • the alkali metal hydroxide is generally employed in catalytic amounts varying from about 0.1 mol.% to about 20 mol.%, preferably in an amount of 10 mol.% based on the ⁇ -ionone quantity.
  • the alkali metal hydroxide may be employed in larger amounts, i.e., up to 100 mol%, although no significant advantages are gained thereby.
  • the alkali metal hydroxide is generally used as an aqueous or lower alkanol solution.
  • the term lower alkanol as used herein connotes straight and branched chain alcohols having from 1-6 carbon atoms.
  • the preferred lower alkanoic solution employed herein is a methanolic solution.
  • the concentration of these solutions can vary from about 5 and about 60 wt.%, preferably between about 20 and 50 wt.%, most preferably about 45 wt.%.
  • the alkali metal hydroxide may also be used in solid form, or as a suspension in a suitable liquid.
  • the process of this invention may be carried out either batchwise or continuously, with the continuous mode being preferred.
  • the remaining amount of catalyst is neutralized, for example with a mineral acid or a lower alkanoic acid.
  • Preferred acids that may be employed are sulfuric, nitric, hydrochloric, acetic and the like.
  • 200 ml of toluene are dosed into the reaction vessel and subsequently the ammonia and the excess acetylene are relieved through an absorption tower.
  • the reactor is emptied and rinsed with 200 ml of toluene.
  • the toluene solution is warmed to about 10° C.
  • the aqueous potassium hydroxide phase is separated off and 500 ml of water are added to the organic phase for the neutralization.
  • the organic phase slowly neutralized to pH 7 with 50% acetic acid while stirring at 10° C.
  • the phases are separated and the aqueous phase is washed once with 300 ml of toluene.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
US05/808,509 1976-07-15 1977-06-21 Process for the preparation of ethynyl-β-ionol Expired - Lifetime US4147886A (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CH9084/76 1976-07-15
CH908476A CH601218A5 (xx) 1976-07-15 1976-07-15

Publications (1)

Publication Number Publication Date
US4147886A true US4147886A (en) 1979-04-03

Family

ID=4348156

Family Applications (1)

Application Number Title Priority Date Filing Date
US05/808,509 Expired - Lifetime US4147886A (en) 1976-07-15 1977-06-21 Process for the preparation of ethynyl-β-ionol

Country Status (10)

Country Link
US (1) US4147886A (xx)
JP (1) JPS6024786B2 (xx)
AT (1) AT357570B (xx)
BE (1) BE856794A (xx)
CH (1) CH601218A5 (xx)
DE (1) DE2731284C2 (xx)
FR (1) FR2358374A1 (xx)
GB (1) GB1525216A (xx)
IT (1) IT1143732B (xx)
NL (1) NL189963C (xx)

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4588849A (en) * 1983-03-11 1986-05-13 Firmenich Sa Process for the preparation of an isomeric mixture of 1-(2,6,6-trimethylcyclohexyl)-hexan-3-ol
US4711875A (en) * 1983-03-09 1987-12-08 Firmenich Sa Composition essentially consisting of trans-1-(2,6,6-trimethylcyclohexyl)-hexan-3-ol
US5637779A (en) * 1994-02-04 1997-06-10 Rhone-Poulenc Nutrition Animale Process for the preparation of vitamin A and new intermediates
CN100371308C (zh) * 2004-10-29 2008-02-27 中国石油化工股份有限公司 由酮和乙炔合成炔醇的方法
WO2016059151A1 (en) * 2014-10-16 2016-04-21 Dsm Ip Assets B.V. Ethynylation of polyunsaturated aldehydes and ketones
WO2020025512A1 (en) 2018-07-30 2020-02-06 Dsm Ip Assets B.V. Catalytic ethynylation

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS54102321A (en) * 1978-01-31 1979-08-11 Ricoh Kk Removing bubbles in lens bonding
JPS54103415A (en) * 1978-01-31 1979-08-14 Ricoh Kk Lens bonding
JPS54103416A (en) * 1978-01-31 1979-08-14 Ricoh Kk Lens bonding

Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2672481A (en) * 1950-11-25 1954-03-16 Eastman Kodak Co Polyene intermediates and methods of making same
US2779799A (en) * 1953-05-12 1957-01-29 Abbott Lab 1-cyclobutyl-1-ethynyl-ethanol-1
US2789130A (en) * 1955-08-24 1957-04-16 Hoffmann La Roche Intermediates and preparation of 6-methyl-9-cyclohexylidene-5-nonen-2-one
US2806067A (en) * 1956-08-02 1957-09-10 Dow Chemical Co Alpha-ethynyl-2, 4, 6-trimethyl-3-cyclohexene-1-methanol
US2919281A (en) * 1958-07-23 1959-12-29 Norda Essential Oil And Chemic Process for the preparation of acetylenic alcohols
US3019265A (en) * 1959-04-02 1962-01-30 Givaudan Corp Process for preparing irones
US3496240A (en) * 1966-09-20 1970-02-17 Hoffmann La Roche Acetylenic carbinol production and recovery by thin film,superatmospheric pressure evaporation with condenser pressure control by venting
US3709946A (en) * 1970-07-31 1973-01-09 Air Prod & Chem Preparation of acetylenic alcohols
US3801653A (en) * 1970-04-21 1974-04-02 Basf Ag Manufacture of acetylene monoalcohols

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1081883B (de) * 1958-02-22 1960-05-19 Basf Ag Verfahren zur Herstellung von AEthinyljonol
US3082260A (en) * 1959-05-20 1963-03-19 Air Reduction Preparation of acetylenic alcohols
NL290214A (xx) * 1962-03-15
US3445534A (en) * 1966-09-06 1969-05-20 Lithium Corp Ethynylating agent and preparation thereof
DE1768877B1 (de) * 1968-07-10 1971-08-26 Basf Ag Verfahren zur kontinuierlichen Herstellung von Acetylenalkoholen
DE2329145B2 (de) * 1973-06-07 1977-02-17 Institut organitscheskoj Chimii imeni N.D. Selinskowo Akademii Nauk SSSR, Moskau Verfahren zur herstellung von alkinolen

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2672481A (en) * 1950-11-25 1954-03-16 Eastman Kodak Co Polyene intermediates and methods of making same
US2779799A (en) * 1953-05-12 1957-01-29 Abbott Lab 1-cyclobutyl-1-ethynyl-ethanol-1
US2789130A (en) * 1955-08-24 1957-04-16 Hoffmann La Roche Intermediates and preparation of 6-methyl-9-cyclohexylidene-5-nonen-2-one
US2806067A (en) * 1956-08-02 1957-09-10 Dow Chemical Co Alpha-ethynyl-2, 4, 6-trimethyl-3-cyclohexene-1-methanol
US2919281A (en) * 1958-07-23 1959-12-29 Norda Essential Oil And Chemic Process for the preparation of acetylenic alcohols
US3019265A (en) * 1959-04-02 1962-01-30 Givaudan Corp Process for preparing irones
US3496240A (en) * 1966-09-20 1970-02-17 Hoffmann La Roche Acetylenic carbinol production and recovery by thin film,superatmospheric pressure evaporation with condenser pressure control by venting
US3801653A (en) * 1970-04-21 1974-04-02 Basf Ag Manufacture of acetylene monoalcohols
US3709946A (en) * 1970-07-31 1973-01-09 Air Prod & Chem Preparation of acetylenic alcohols

Non-Patent Citations (5)

* Cited by examiner, † Cited by third party
Title
A. G. Viehe "Chem. of Acetylenes", pp. 225-226 (1969), Marcel Dekker, New York, N.Y. *
Houben-Weyl, "Methoden der Organ. Chemie", Bd. VII/2b, Teil II, pp. 1974-1975 (1976). *
Oroshnik et al., "J.A.C.S.", vol. 71, pp. 2062-2065 (1949). *
Shachat et al., "J. Org. Chem.", vol. 27, pp. 1498-1504 (1962). *
Tedeschi et al., "J. Org. Chem", vol. 28, pp. 1740-1743 (1963). *

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4711875A (en) * 1983-03-09 1987-12-08 Firmenich Sa Composition essentially consisting of trans-1-(2,6,6-trimethylcyclohexyl)-hexan-3-ol
US4588849A (en) * 1983-03-11 1986-05-13 Firmenich Sa Process for the preparation of an isomeric mixture of 1-(2,6,6-trimethylcyclohexyl)-hexan-3-ol
US4626381A (en) * 1983-03-11 1986-12-02 Firmenich Sa Process for the preparation of an isomeric mixture of 1-(2,6,6-trimethylcyclohexyl)-hexane-3-ol
US5637779A (en) * 1994-02-04 1997-06-10 Rhone-Poulenc Nutrition Animale Process for the preparation of vitamin A and new intermediates
CN100371308C (zh) * 2004-10-29 2008-02-27 中国石油化工股份有限公司 由酮和乙炔合成炔醇的方法
WO2016059151A1 (en) * 2014-10-16 2016-04-21 Dsm Ip Assets B.V. Ethynylation of polyunsaturated aldehydes and ketones
WO2020025512A1 (en) 2018-07-30 2020-02-06 Dsm Ip Assets B.V. Catalytic ethynylation
CN112399968A (zh) * 2018-07-30 2021-02-23 帝斯曼知识产权资产管理有限公司 催化乙炔化

Also Published As

Publication number Publication date
FR2358374B1 (xx) 1983-10-21
IT1143732B (it) 1986-10-22
NL189963B (nl) 1993-04-16
NL7707395A (nl) 1978-01-17
DE2731284C2 (de) 1987-04-09
DE2731284A1 (de) 1978-01-19
NL189963C (nl) 1993-09-16
CH601218A5 (xx) 1978-06-30
GB1525216A (en) 1978-09-20
JPS539747A (en) 1978-01-28
ATA506477A (de) 1979-12-15
AT357570B (de) 1980-07-25
FR2358374A1 (fr) 1978-02-10
BE856794A (fr) 1978-01-16
JPS6024786B2 (ja) 1985-06-14

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Owner name: ROCHE VITAMINS INC., NEW JERSEY

Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNOR:HOFFMANN-LA ROCHE INC.;REEL/FRAME:008366/0982

Effective date: 19970106